JPH01106047A - Color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility and to enhance the saturation and hue of a formed color positive image by laminating red-, green- and blue- sensitive silver halide emulsion layers on a support and incorporating a specified dye. CONSTITUTION:This sensitive material has at least on red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer on the support and contains at least one kind of dye represented by formula I (where each of X<1> and X<2> is H, cyano, etc., each of Y<1> and Y<2> is H, an aliphat. group, etc., each of L<1>-L<3> is methine, m=0, 1 or 2, M<n+> is an n-valent cation and n=1 or 3). The sensitive material has improved color reproducibility and the saturation and hue of a color positive original are more faithfully reproduced by a formed color positive image.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a positive-positive type silver halide color photographic light-sensitive material used to obtain a color positive image from a color positive original. The present invention relates to a positive-positive type silver halide color photographic light-sensitive material in which reproduction is improved and the saturation and hue of a color positive image to be formed are improved so as to more faithfully reproduce the chroma single hue of a color positive original.

(Prior Art) A silver halide color photographic light-sensitive material generally has a silver halide emulsion layer that is sensitive to each of the 3JX colors of blue, green, and red.
By developing yellow, magenta, and cyan respectively, a color image is reproduced using the so-called subtractive color method.

Therefore, the reproduced color image is affected by the wavelength range to which each layer is sensitive (spectral sensitivity distribution), and is also greatly influenced by the yellow, magenta, and cyan hues produced by each layer, that is, the spectral absorption characteristics of the coloring pigments. . Generally, these characteristics do not fully satisfy the theoretically possible ideal system due to various restrictions on the materials used.

For example, regarding the problem of spectral sensitivity distribution, great efforts have been made to improve the spectral sensitivity distribution, including the development of new sensitizing dyes. Furthermore, even when the same sensitizing dye is used, it is known that the spectral sensitivity distribution changes depending on the characteristics of the silver halide emulsion used, the environment in which the sensitizing dye is adsorbed to the silver halide, etc. For example, JP-A-61-103149, JP-A-61-13394
No. 1 states that excellent spectral sensitivity characteristics can be obtained by using a sensitizing dye during the preparation of a silver halide emulsion. Furthermore, it is known that the spectral sensitivity distribution is also affected by the dye used in the photosensitive material.

These dyes have been studied for anti-irradiation and anti-halation purposes, particularly with the aim of improving sharpness. Examples of such dyes include oxonol dyes, azo dyes, and anthraquinone dyes, but care must be taken when selecting dyes so that the addition of dyes does not adversely affect photographic properties. In addition to shelf life, special consideration must be given to decolorization and elution characteristics during processing; if these characteristics are insufficient, dye absorption may remain in the formed image, resulting in image staining. be.

(Problems to be Solved by the Invention) However, even if any of the conventional proposals for improving the spectral sensitivity distribution is used, it is still difficult to obtain color reproduction that satisfies the requirements.

This was particularly noticeable in positive-positive type silver halide color photographic materials.

Positive-positive type silver halide color photographic materials used to directly obtain a color positive image from a color positive original include, for example, a color reversal film using a reversal process, a color duplicating film, a color reversal vapor, and an auto-positive color photosensitive material. Examples include auto-positive color film, auto-positive color vapor, diffusion transfer type instant film, and diffusion transfer type tricolor vapor, but these positive-positive type silver halide color photographic light-sensitive materials are particularly sensitive to their spectral sensitivity. It was difficult to design the distribution.

A major obstacle in designing the spectral sensitivity distribution of color positive silver halide color photographic materials lies in the variety of color positive originals used. Items used as color originals include, for example, external color slide film, internal color slide film, transparent color positive originals such as movie positive film, color photographic prints, color prints, illustrations, paintings, and even real objects. Examples include reflective color positive originals. The coloring materials that form these diverse images include azomethine dyes, azo dyes,
There are a wide variety of pigments, including organic pigments and inorganic pigments, and the spectral absorption of these coloring materials is wide-ranging.Moreover, there is a possibility that coloring materials that could not be anticipated at the time of sensitive material design may be developed and used.

The difficulty this poses in designing the spectral sensitivity distribution of a positive-positive type silver halide color photographic light-sensitive material becomes clear when compared with, for example, the case of a negative-positive type silver halide photographic light-sensitive material. In other words, in the case of a negative-positive system, all originals used for printing are negative films,
The image consists mostly of azomethine dye (coupled product of coupler and developing agent). Therefore, it can be said that the color absorption spectrum is almost uniform, although there are some differences depending on the type of sensitive material.The spectral sensitivity distribution of negative-positive light-sensitive materials is based on the uniform absorption For example, in the case of color vapors, by taking advantage of this design, the spectral sensitivity of the red-sensitive layer can be shifted to extremely long wavelengths to achieve a good separation from the spectral sensitivity of the green-sensitive layer. It has good color reproduction.

Furthermore, since the negative film itself is not intended to be observed, it is also possible to select the absorption spectrum of one coloring dye by considering only the color reproduction during printing.

It can be said that the coloring pigments of current color and negatives are selected from this viewpoint.

On the other hand, many color positive originals were designed without the expectation that they would be copied using positive-positive silver halide color photosensitive materials, and the coloring materials used in color positive originals themselves They are completely freely selected within a range that provides good color reproduction. Positive-positive silver halide color photographic materials are required to faithfully reproduce the colors of these various coloring materials, and this requires the spectral sensitivity distribution of positive-positive silver halide color photographic materials. This means that it needs to be as wide as possible. Balancing this with improving the distribution of spectral sensitivity among the red, green, and blue color sensitive layers in order to improve color reproduction was technically an extremely difficult task.

In addition, Japanese Patent Application Laid-open No. 52-20830 describes wavelengths of 580 to 6.
A color light-sensitive material containing a bispyrazolone pentamethine oxonol water-soluble dye having a spectral absorption maximum in the 30 nm range is described. If this dye is used, the spectral sensitivity distribution of the red- or green-sensitive layer will be improved, and the effect of improving one-color reproducibility will be seen. There were many problems that needed to be solved, such as the dye color tending to remain in the image after the processing described above.

JP-A No. 51-1419 discloses a bispyrazolone monomethine oxonol dye that has an absorption maximum at a wavelength shorter than 440 nm and can absorb short wavelength blue light from 390 to 440 nm.
It has been described that the spectral sensitivity distribution of a blue-sensitive emulsion layer is improved by using a bispyrazolone trimethine oxonol dye having an absorption maximum in the range from 60 to 520 nm. However, in this case as well, the dye inhibits spectral sensitization and deteriorates the storage stability of the photosensitive material, and there are many similar problems such as the color of the dye tends to remain in the image after processing.

Therefore, the first object of the present invention is to improve color reproduction, and to enable the saturation and hue of the formed color positive image to more faithfully reproduce the saturation and hue of a color positive original. The purpose is to provide materials.

A second object is to provide a positive-positive type silver halide color photographic light-sensitive material that can reproduce colors more faithfully to any of a variety of color positive originals containing different coloring materials.

An object of the present invention is to provide a positive-positive type silver halide color photographic light-sensitive material with excellent color reproduction in which a color positive image formed after processing is not contaminated by incomplete decolorization of dye.

(Means for Solving the Problems) These objects of the present invention have at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer on a support, each having the following general formula (I This was achieved by a positive-positive type silver halide color photographic light-sensitive material containing at least one dye represented by:

General formula (I) (wherein, Xl and Xl are each a hydrogen atom, a cyano group, -OR
, -COOR', -COR', -CONRR, -NR' R2, 1° 2l -NRCOR, -NRSOz R2 represents an aliphatic group, an aromatic group or a heterocyclic group, and yl and y2 each represent a hydrogen atom, an aliphatic family group, aromatic group, heterocyclic group, -NR3R',
-NR3COR' 3[-NR5o2R, z
, z are each a hydrogen atom, -, /7/ group, -CONR
5R6, -COOR, -COR5, -NR5R6, -N
RCOR, -NR" So R, -SO□R5, represents a sulfonic acid group, an aliphatic group, an aromatic group or a heterocyclic group,
t, 1, t, 2, t, 3 represent a methine group, m represents 0, 1 or 2, M represents an n-valent cation, n represents an integer of 3, R1, R
2, R3, R4, R5 and R6 each represent a hydrogen atom, an aliphatic group, an aromatic group, or l 2 3 4 represents a heterocyclic group, and R and R, R and R, or R5 and R6 are connected to form 5 or It may form a 6-membered ring (eg, morpholine ring, piperidine ring). ) General formula (I) will be explained in more detail.

Xl, Xl, Yl, Y2, Zl, Z2. R1, R, R,
The aliphatic groups represented by R, R and R6 preferably have 1 to 12 carbon atoms, and each is an unsubstituted alkyl group (for example, methyl, ethyl, propyl, isopropyl, t-butyl,
n-octyl, n-dodecyl, n-hexyl), substituted alkyl groups (for example, the following groups are mentioned. Substituents include F, C, Br, etc. halogen atoms (for example, 2-
chloroethyl, trifluoromethyl, difluoromethyl, 1,1,2.2-tetrafluoroethyl, 2-bromoethyl), phenyl groups (e.g. benzyl, phenethyl,
4-chlorobenzyl, 4-methoxybenzyl, 4-sulfopropyloxybenzyl, 2-sulfobenzyl, 4-
Sulfophenethyl, 2,4-dihydroxybenzyl.

4-carboxybenzyl), hydroxy group (e.g. 2
-hydroxyethyl, 3-hydroxypropyl), cyano groups (e.g. 2-cyanoethyl), carboxylic acid groups (e.g. carboxymethyl, carboxyethyl, 4-carboxybutyl), sulfonic acid groups (e.g. sulfomethyl, 2-sulfoethyl, 4-sulfobutyl), alkoxy groups (e.g. 2-methoxyethyl, 2-(2-hydroxyethoxy)ethyl, ethoxyethyl)) or cycloalkyl groups (e.g. cyclopentyl, cyclohexyl)
represents.

xi, x2, yl, y2, zl, z2,
The aliphatic groups represented by R1, R, R, R, R and R6 are each preferably substituted or unsubstituted and have 1 to 4 carbon atoms.
alkyl groups (e.g. methyl, ethyl, n-propyl,
n-butyl, isopropyl, t-butyl, 2-hydroxyethyl, 2-methoxy or ethoxyethyl, 3-methoxypropyl, cyanomethyl, carbamoylmethyl, carbamoylmethyl, acetylmethyl, carboxymethyl, 2-sulfoethyl, 4-sulfobutyl, tri fluoromethyl, benzyl, 2-sulfobenzyl, phenethyl)
represents.

xi, x2. yl, 'v2, zl, z2. R1, R2
, R3, R4, R5 and R6 preferably have 6 to 12 carbon atoms, and each is an unsubstituted aryl group (e.g. phenyl group, naphthyl group) or a substituted aryl group (e.g. the following groups). 0M substituents that may be mentioned include sulfonic acid groups (e.g. 3-sulfophenyl, 4-sulfophenyl).

2,5-disulfophenyl), carboxylic acid groups (e.g. 4
-carboxyphenyl), alkoxy groups (e.g. 4-methoxyphenyl, 4-(3-sulfopropyloxy)
phenyl, 4-methoxy-3-sulfophenyl), alkyl groups (e.g. p-tolyl, 2-methyl-4-sulfophenyl), halogen atoms (e.g. 4-chlorophenyl,
3.5-dichlorophenyl), hydroxyl group (e.g. 3-hydroxyphenyl, 4-hydroxyphenyl), amino group (e.g. p-dimethylaminophenyl, p-dimethylaminophenyl), cyano group (e.g. p-cyanophenyl)). represent.

xl, X2, Yl, Y2, zl, zz, R1゜R2,R
The aromatic groups represented by 3, R4, R5 and R6 are each preferably a substituted or unsubstituted phenyl group (for example,
Phenyl, 4-hydroxyphenyl, 4-sulfophenyl, 3-carboxyphenyl, tolyl, 4-chlorophenyl, 3-methoxyphenyl, 3-ethoxyphenyl,
4-carbamoylphenyl).

xi, xl, yl, Y2. zl, z2. R1゜R2,
The heterocyclic groups represented by R3, R4, R5 and R6 each include a 5- to 6-membered heterocyclic group containing at least one nitrogen atom (e.g., 2-pyridyl group, 5-sulfobenzimidazol-2-yl group, 5- to 6-membered heterocyclic group). -Carboxybenzothiazole-
2-yl group, morpholino group, piperidino group),
The number of carbon atoms is preferably 2 to 10. A 5.6-membered ring containing at least one C and at least one N is preferable, and may contain O, S, and Se in addition to N as a petro atom.

The methine group represented by Ll, R2, and R3 has a substituent (
For example, it may have a methyl, ethyl, phenyl, or chlorine atom).

M0Φ is monovalent (where n represents an integer from 1 to 3,
) represents a cation such as Ho, NaΦ, Ni', C
a2Φ, N H4e.

IN (CH)’, (”C4H9)4N.

etc.

The cation M0@ may be an N-substituted ammonium salt as described above, and organic amines such as triethylamine and pyridine can be selected as the amine for forming this ammonium salt. In addition, the cation is NH (
When C2H5)3, one exemplified compound is described as an amine adduct of hydroxypyridone rather than an oxonol salt. The same applies to other ammonium salts hereinafter.

When the general formula (I) has a sulfonic acid group or a carboxylic acid group, these may be used as a free acid or as a salt (e.g. Na, %N
Inorganic salts such as H4 or organic amine salts such as triethylamine salts and pyridinium salts) may be formed.

Specific examples of the dye represented by general formula (I) are shown below, but the present invention is not limited thereto.

qμ5 nC4H9 2H5 C2I (5 C4H9 2HS H3 H2S03 exposed C4H9 H3' C4H9 C2) (4SO3NaC2) (4S03NaCAC2H
5 C8A (C1 (2) 4SO3Na (C1 (2) 4S03N & S, A trajectory C exclusive OHCH,, C1 (20H CH2C02HC) (2CH20I ( l C2H5C2H5 C2H5C2H5 CH3 s03 to 803K CH2CH20HCH2C) I20H CH 2CH25O3K “2CH2SQ, niC )
The absorption maximum of the above dye is shown below.

The dye represented by the general formula (I) can be prepared according to the synthesis example shown below, and also as described in British Patent No. 1,278゜621, British Patent No.
, 512,863 and 1,579.899.

Synthesis Example 1 Synthesis of Dye 1 1-ethyl-6-hydroxy-4-methyl-3-sulfomethylpyrid-2-one sodium salt 4.0 g, pentadiencyanyl hydrochloride 2.1 g, triethylamine 5
．． 1.6 ml of acetic anhydride was added dropwise into a mixture of 0 ml and 120 ml of isopropyl alcohol, and the mixture was stirred overnight at room temperature. The generated precipitate was collected by filtration, and water/methanol = 1/3
Dissolve in mixed solvent 807i. An ethanol solution containing 1.4 g of potassium acetate was added dropwise to this solution, and the resulting precipitate was collected by filtration and dried under reduced pressure. Yield: 1.1 g, maximum absorption in water: 692 nm, melting point: 300° C. or above Synthesis Example 2 Synthesis of Dye 26 3.5 g of 3-carbomethoxy-4,6-cyhydroxy-1-phenylpyrid-2-one, 1.
3g of triethylamine and 4.1ml of triethylamine were dissolved in 50ml of methanol, and 1.3ml of acetic anhydride was added thereto. This solution is stirred at room temperature for 2 hours, and the formed precipitate is collected by filtration. This was purified with methanol-isopropyl alcohol, and after drying, 2.7 g of dye 26 was obtained. Maximum absorption in dilute aqueous alkali solution: 528 nm, melting point: 300°C or higher 3-cyano-1,2-dihydro-4-methylpyridin-2-one 3
．． 0g, l, 3.3-trimethoxypropene 1.3g,
A solution of 2.8 ml of triethylamine in ethanol is heated under reflux for 2 days. The mixture was cooled to room temperature, and the precipitate was filtered and dried to obtain 1.5 g of dye 19. Maximum absorption in water: 587 nm 5.4 g of 3-cyano-1-ethyl-6-hydroxy-4-methylpyrid-2-one, 4.5 g of 3-methylpentadiene cyanyl hydrochloride, 6.9 g of triethylamine, 50 d of methanol and lower the room temperature to below 5°C. 3.1 ml of acetic anhydride is added dropwise to this solution, and the mixture is stirred at room temperature for 13 hours.

The generated precipitate was collected by filtration and mixed with 50 d of acetonitrile,
After heating and washing with 1.0 ml of triethylamine, the precipitate was dried to obtain 1.9 g of Dye 12. Absorption maximum in N,N-dimethylformamide 730 nm, melting point 198~
204°C Synthesis Example 5 Synthesis of Dye 29 1-Ethyl-6-hydroxy4-methyl-3-sulfomethylpyrid-2-one 3.0 g of 1,000-monosodium salt, 0.8 g of ethyl orthoformate, 2.0 g of triethylamine. The mixture of the three slides is heated under reflux in 50 ml of ethanol for 8 hours.

This solution was concentrated under reduced pressure, dissolved in a mixed solvent of methanol 107i and ethanol 10, and dissolved in 10% potassium acetate.
20TIIIl of ethanol solution! Drip. Filter the formed precipitate.

When washed with ethanol, dye 29 becomes 1. ．． 5 [obtained. The positive-positive type silver halide color photographic light-sensitive material of the present invention is capable of forming a color positive image directly from a color positive original without the need for an intermediate medium such as a negative. All materials used for the above purposes, regardless of their method, belong to the positive-positive type silver halide color photographic materials of the present invention. Examples of positive-positive type silver halide color photographic light-sensitive materials include inner color reversal film, outer color reversal film, color duplicating film, color reversal vapor, autopositive color film using autopositive method, Examples include auto-positive color vapor, diffusion transfer type instant film, and diffusion transfer type dry color vapor, but are not limited to these examples.

According to the above regulations, for example, color vapors, color positive films, color negative films, etc. using ordinary negative emulsions do not belong to the positive-positive silver halide color photographic light-sensitive materials of the present invention.

The dye represented by general formula (I) used in the present invention can be introduced into the hydrophilic colloid layer by a conventional method. When adding the dye to a photographic emulsion layer, add an aqueous solution of the dye at an appropriate concentration to the silver halide emulsion before coating, and when adding the dye to a non-light-sensitive layer, add the dye to an aqueous solution of a woody colloid. An aqueous solution may be added and these liquids may be applied onto a support or onto a layer constituting a photographic material by a known method.

Further, to explain in more detail the method of introducing the dye represented by the general formula (I) into the wood-philic colloid layer, the dye can be directly dispersed into the emulsion. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, lysine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution. Also, this U.S. Patent No. 3.469.
987, etc., by dissolving the dye in a volatile organic solvent and dispersing the solution in a woody colloid;
A method of adding this dispersion to a wood-loving colloid, Tokuko Sho 4
No. 6-24185, etc., in which the dye is dispersed in an aqueous solvent without being dissolved, and the dispersion is added to a woody colloid: US Pat. No. 3,822.
A method such as that described in No. 135, in which a dye is dissolved in a surfactant and the solution is added to a wood-philic colloid, is used.

In addition, for addition to hydrophilic colloids, JP-A-51-7
4624, JP-A-5O-8082fS, U.S. Patent No. 2,912,343, U.S. Pat. No. 3.342.605, U.S. Pat. No. 2,996,287, U.S. Pat. The following method is also used.

Preferred embodiments of the positive-positive type silver halide color photographic light-sensitive material of the present invention are as follows.

(1) i) The wavelength showing the maximum spectral sensitivity of the red-sensitive emulsion layer is on the longer wavelength side than 580 nm, and the wavelength corresponding to 30% of the maximum spectral sensitivity is on the shortest wavelength side. is on the longer wavelength side than 560 nm, and ii) the wavelength showing the maximum spectral sensitivity of the green-sensitive emulsion layer is on the shorter wavelength side than 580 nm, and the wavelength corresponding to 30% of the maximum spectral sensitivity is Among them, the longest wavelength is on the shorter wavelength side than 590 nm.

(2) i) The wavelength showing the maximum spectral sensitivity of the green-sensitive emulsion layer is on the longer wavelength side than 500 nm, and the wavelength corresponding to 30% of the maximum spectral sensitivity is on the shortest wavelength side. is on the longer wavelength side than 480 nm, and ii) the wavelength showing the maximum spectral sensitivity of the blue-sensitive emulsion layer is on the shorter wavelength side than 500 nm, and the wavelength corresponding to 30% of the maximum spectral sensitivity is Among them, the longest wavelength is on the shorter wavelength side than 510 nm.

How to define and express the relative sensitivity at each wavelength in spectral sensitivity is described in The Theory of the Photographic Process by James (T.

! +, Jatmes, The Theory
of the Photographic Pr
The method described in Vol. 4, p. 510 was followed.

The present invention is further preferred.

i) The wavelength showing the highest spectral sensitivity of the red-sensitive emulsion layer is 6.
00 nm, the shortest wavelength among the wavelengths corresponding to 30% of the maximum spectral sensitivity is on the longer wavelength side than 590 nm, and ii) the spectral sensitivity of the green-sensitive emulsion layer. A positive-positive type in which the wavelength showing the highest sensitivity is on the shorter wavelength side than 560 nm, and the longest wavelength among the wavelengths corresponding to 30% of the maximum spectral sensitivity is on the shorter wavelength side than 570 nm. It is a silver halide color photographic material.

Also, more preferably.

i) The wavelength showing the highest spectral sensitivity of the green-sensitive emulsion layer is 5.
ii) the spectral sensitivity of the blue-sensitive emulsion layer; A positive-positive type in which the wavelength showing the highest sensitivity is on the shorter wavelength side than 480 nm, and the longest wavelength among the wavelengths corresponding to 30% of the maximum spectral sensitivity is on the shorter wavelength side than 500 nm. It is a silver halide color photographic material.

In the above preferred embodiment, the wavelength showing the maximum spectral sensitivity of each color-sensitive emulsion layer and the maximum spectral sensitivity of 30
% of the wavelengths that are not specified, the performance as a positive-positive silver halide color photographic light-sensitive material is satisfied.

For example, the wavelength showing the highest spectral sensitivity of the red-sensitive emulsion layer is generally 7.
It is preferable that the wavelength on the long wavelength side of the wavelength corresponding to 30% of the maximum spectral sensitivity is on the shorter wavelength side than 750 nm.

British Patent No. 1,278,621 describes the synthesis and uses of oxonol dyes, and includes a general enumeration of the uses of the dyes in photographic systems, including positive-positive silver halide color photography. There is no disclosure whatsoever regarding the photosensitive material.

Furthermore, British Patent No. 1,521,083 describes the use of hydroxypyridone oxonol dyes in photographic materials. According to the compounds or methods of use described herein, an antihalation layer having broad absorption over the entire visible range is formed, as is clear from the text and examples. This utilizes the completely opposite property from the viewpoint of the effect of the positive-positive type silver halide color photographic light-sensitive material of the present invention.

According to a preferred embodiment, the positive-positive silver halide color photographic light-sensitive material of the present invention contains a dye represented by general formula (I), and one or more of the sensitizing dyes represented by general formula (II) below. It comprises at least one red-sensitive silver halide emulsion layer sensitized by a combination of two or more.

General formula (■) Here, Wl and Wl represent a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle by condensing a benzene ring or a naphthalene ring, and Pl is a hydrogen atom, or a substituted or Unsubstituted alkyl group.

Represents an aralkyl group or a substituted or unsubstituted aryl group.

P and P3 are an alkyl group, or a sulfur group,
Represents a hydroxy group, a carboxy group, a sulfophenyl group, a carboxyphenyl group, an alkoxy group, a phenyl group, or an alkyl group substituted with a halogen atom, and P2
Alternatively, at least one of P3 is a group having a hydroxy group, a sulfo group, or a carboxy group. n is 0.1.
2, and l each represents 0 or 1,
Here, 10 sentences≠O for n+. ) The use of compounds represented by the general formula (n) alone or in combination as a sensitizing dye in the red-sensitive emulsion layer is effective in broadening the spectral sensitivity distribution and improving color reproduction. However, these dyes are known to be desorbed from the silver halide immediately after coating or as the material ages, depending on the dye coexisting in the photosensitive material, changing the photographic performance. It was observed that when the dye described in 1.
) A positive-positive type silver halide color photographic light-sensitive material with improved one-color reproduction can be obtained.

According to a preferred embodiment of the present invention, the positive-positive silver halide color photographic light-sensitive material of the present invention comprises at least one red-sensitive emulsion layer; This is a positive-positive type silver halide color photographic light-sensitive material comprising one or more layers closer to the direction of incident light during printing than the emulsion layer or the red-sensitive emulsion layer. The dye represented by general formula (I) is contained in one or more of the above layers, and can also be contained in other layers.

According to the above aspect of the present invention, it is preferable that the dye represented by the general formula (I) has spectral absorption with a half-width limited to a wavelength range required depending on the purpose, and if the absorption band is too broad, red sensitivity This is undesirable because it causes an unnecessary decrease in the sensitivity of the emulsion layer.

According to a preferred embodiment of the present invention, the positive-positive silver halide color photographic light-sensitive material of the present invention has an absorption maximum of 550 nm to 650 nm among dyes represented by general formula (I).
m, and its half-width is 120 nm or less.

According to another preferred embodiment of the present invention, the positive-positive silver halide photosensitive material of the present invention has a dye represented by general formula (I) whose absorption maximum is between 450 nm and 550 nm, and whose half-value width is between 450 nm and 550 nm. contains those with a diameter of 120 nm or less.

Here, the above absorption maximum and half-value width are obtained by applying a gelatin solution containing the dye represented by the general formula (I) on a transmission base at a gelatin coating amount of 5 g/rn', and the absorption maximum shown by the dye represented by the general formula (I). This is the value obtained when the coating amount is adjusted so that the density value of is 1.

General formula (1,) used according to this preferred embodiment
A relatively highly soluble dye that does not aggregate in the gelatin layer is preferably used as the dye. Conventionally, dyes that aggregate in the gelatin layer and cover the entire visible range have been used, but the present invention utilizes the opposite effect to the use of such dyes.

The amount of the dye of general formula (I) contained in the positive-positive silver halide color photographic light-sensitive material of the present invention is preferably such that the spectral absorption density at least at its maximum absorption wavelength is 0.3 or more. The amount of dye to be contained in order to provide an absorption density in a range of 1 to 1000 mg/If is appropriate, and preferably 5 to 250 mg/rn'
It is. The amount of this dye to be used is determined within the range necessary for improving color reproduction.

According to a preferred embodiment of the present invention, the positive-positive type silver halide color photographic light-sensitive material of the present invention contains a dye represented by the general formula (I), and is prepared using a subtractive color method from a color positive original.
This is a positive-positive type silver halide color photographic light-sensitive material that is exposed using M and C filters.

According to a preferred embodiment of the present invention, the positive-positive type silver halide color photographic light-sensitive material of the present invention is a color reversal vapor containing a dye represented by general formula (I).

Two general configurations of color reversal vapors are shown below.

Structure 1 (1) Scratch prevention layer (2) UV-absorbing compound layer (31 blue sensitized emulsion + yellow-forming coupler (4) intermediate sensitive layer (5) green sensitized emulsion + magenta-forming coupler (6) medium Sensitive layer (7) Red sensitized emulsion + cyan forming coupler (8) Polyethylene coated paper support structure r&2 (1) Scratch prevention layer (2) UV absorbing compound layer (3) Green sensitized emulsion + magenta forming Coupler (4) Neutral sensitive layer (5) Red sensitized emulsion + cyan forming coupler (6) Neutral sensitive layer (7) Blue sensitized emulsion + yellow forming coupler (8) Polyethylene coated paper support In structure 2, Silver bromoiodide with tabular grains is used so that the red and green sensitized emulsions are less sensitive to blue light.Silver bromoiodide emulsions with tabular grains are well known, especially in JP-A-Sho. No. 58-113928, U.S. Patent No. 4,4
No. 34,226.

The dyes of general formula (I) of the present invention can be used in any one or more of the layers of configuration 1 and configuration 2.

Further, the dye is preferably used in each of the layers of Structure 1 and Structure 2, in the red-sensitive emulsion layer and in one or more layers closer to the exposure light incident side than the red-sensitive emulsion layer.

Moreover, each of the above layers can be provided separately into two or more layers, if necessary.

In addition to printing from slides, color reversal vapor can be used to print from prints, print from prints, and print from actual objects, and the spectral sensitivity of the positive-positive printing sensitive material mentioned earlier. It is a typical sensitive material that is difficult to design.

According to a preferred embodiment of the present invention, the positive-positive type silver halide color photographic light-sensitive material of the present invention is an autopositive color film and an autopositive color vapor containing a dye represented by general formula (I).

Like the color reversal vapor, these photosensitive materials are typical photosensitive materials that have the difficulty of designing the spectral sensitivity of the aforementioned positive-positive printing photosensitive materials.

The silver halide emulsion used in the present invention is prepared by mixing a solution of a water-soluble silver salt (for example, silver nitrate) and a water-soluble halide salt (for example, potassium bromide, sodium chloride, potassium iodide alone or in a mixture thereof) with gelatin. It is produced by mixing in the presence of a water-soluble polymer solution such as In addition to silver chloride and silver bromide, typical silver halides produced in this manner include mixed silver halides 1 such as silver chlorobromide, silver chloroiobromide, and silver iodobromide. Silver halide grains may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may have a uniform phase throughout the grain, or may have a mixture of these. You can leave it there.

For example, for silver iodobromide grains with different phases,
The grain may have a core or single or multiple layers rich in silver bromide than the average halogen composition, or may have a core or single or multiple layers rich in silver iodide than the average halogen composition. Particles may have a layer within the particle,
Therefore, the surface layer of one grain may be covered with a layer richer in silver bromide than the average halide composition, or a layer richer in silver iodide than the average halide composition. In the case of cubic particles, the particle diameter is taken as the grain size, and in the case of cubic particles, the particle size is taken as the ridge-long particle size. Based on the projected area (expressed as an average), it is preferably 4 tons or less and 0.1 g or more, but it is particularly preferable to The particle size distribution may be narrow or wide. A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 90% or more, especially 95% or more of all grains are within ±40% of the average grain size in terms of grain number or weight can be used in the present invention. can. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodispersed silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in an emulsion layer having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The silver halide grains used in the present invention may have regular crystal shapes such as cubes, octahedrons, dodecahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical shapes. or a composite form of these crystal forms.

Tabular grains may also be used, especially tabular grains with a length/thickness ratio of 5 or more, especially 8 or more, which accounts for 50% of the total projected area of the grain.
An emulsion having a concentration of more than 100% may be used.

These various emulsions may be a mixture of these various crystal forms, and may be either a surface latent image type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention includes P, graphide (P,
Glafkides), Shimmy Ko.
Photographic (Chimie et Physi
quePhotographique), published by Paullontel (1967),
G. F. Duffin, Photographic Emulsion Chemistry (Ph.
otographicEmulsion Chemises
Try), Focal Pres
s) (1966), V, L, Zelikman (V, L
, Zelikman et al., Making and Coating Photographic Emulsions (Ma.
King and Coating Photogra
phicEmulsion), published by Focal Press (1964). That is, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, ie, the so-called Chondrald double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (e.g. ammonia, rhodankali or U.S. Pat. No. 3,271,157, JP-A-5
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, or JP-A-54-155828). Physical ripening results in a monodisperse emulsion with a regular crystalline form and a near-uniform grain size distribution. In order to remove soluble silver salts from the emulsion before and after physical ripening, noodle washing, flocculation sedimentation method, ultrafiltration method, etc. are used.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination.

Namely, sulfur sensitization using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines); , hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal compounds (e.g., total complex salts, Pt,
A noble metal sensitization method using complex salts of metals of group (I) of the periodic table, such as Ir, Pd, Rh, and Fe, can be used alone or in combination.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, androle nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are condensed to these nuclei, ie, indolenine nucleus and benzindolenine nucleus.

Indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, natutoimidazole nucleus, quinoline nucleus.

An imidazo[4,5-b]quinoline nucleus or the like can be applied.

These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
,4-')one nucleus, thiazolidine-2,4-dione nucleus,
Rhodanine nucleus, thiobarbic acid nucleus, 2-thioselenazolidine-2゜4-dione nucleus, pyrazolo[1,5-a]
A 5- to 6-membered heterocyclic nucleus such as a benzimidazole nucleus and a pyrazolo[5,1-bl quinazolone nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
For example, the emulsion may contain a substance exhibiting supersensitization.
Aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (
For example, U.S. Pat.
, 721), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent Section 3,615.613;
The combinations described in 3,615,641, 3,617,295 and 3,635,721 are particularly useful.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles (preferably 5-nitrobenzimidazoles), nitroindazoles, benzotriazoles (preferably 5-methylbenzotriazoles) , triazoles, etc.: Mercapto compounds, such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptobenzoxasols, mercaptooxadiazoles, mercaptothiadiazoles, mercaptotriazoles, mercaptotetrazoles (especially l -phenyl-5-nimerkabuto, tetrazole, etc.), mercaptotriazines, mercaptotriazines, etc.: For example, thiocarbonyl compounds such as oxazolinthione; -(1,3
, 3a, 7) tetraazaindene), pentaazaindene, etc.: benzenethiosulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides: purines such as adenine, etc. Known as antifoggants or stabilizers. Many compounds can be added.

For more specific examples of antifoggants or stabilizers and their uses, see, for example, U.S. Patent Section 3,954;
No. 474, No. 3,982,947, Special Publication No. 52-28
No. 660, RD17643 (December 1978) VI
A-VIM and E, J. Barr (formerly E, J., rr), Stabilization of Photographic Shifflebar Halide Emulsions (5tabili)
zation of Photographic 5i
lver Halide Emulsion)
, Focal Press,
(published in 1974), etc.

The photosensitive material produced using the present invention may contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenols as color antifogging agents or mixing inhibitors. It may also contain derivatives and the like.

In the silver halide emulsion used in the present invention, the silver halide grains contain 2 mol % or more of silver chloride, and the area ratio of crystal planes with a Miller index (100) is expressed by the relation % % (wherein, is measured by X-ray diffraction diffraction method (20
This is the intensity ratio of the respective diffraction lines belonging to the 0) plane and the (222) plane, that is, it is expressed as: ) Monodisperse silver chlorobromide which satisfies the following is not preferred because it is difficult to sufficiently reproduce a white background when used in a positive-positive halogen light-sensitive material.

In the present invention, an internal latent image type silver halide emulsion which has not been fogged in advance can be used.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, a silver halide emulsion is deposited on a transparent support at a concentration of 0.5 as silver.
~3 g/m'', exposed for a fixed time of 0.01 to 10 seconds, and developed in the following developer A (internal type developer) at 18°C for 5 minutes to obtain a normal photographic density. The maximum density measured by the measuring method was determined by applying the same amount of silver halide emulsion and exposing it in the same manner as above using the following developer B.
It is preferable to have a density that is at least 5 times greater, more preferably at least 10 times greater than the maximum density obtained when developed for 6 minutes at 20° C. in a surface developer.

Internal developer A Metol 2g Sodium sulfite (
anhydrous) 90g hydroquinone
8g Soda carbonate (-water salt) 52
．． 5gKBr 5gKI
O, add 5g water
1 standing surface developer B metol 2.5g L-ascorbic acid logN a B Oz 4 H
z O35gKBr
As a specific example of a latent emulsion, for example, British Patent No. 1.011,06
No. 2 and U.S. Patent Section 2.592.250, 2.
No. 456,943, Special Publication No. 58-54379, No. 58
-3536, eO-5582, JP-A-52-15
No. 6614, No. 57-79940, No. 58-7022
Conversion-type silver halide emulsions described in the specification of No. 1 and shelled emulsions thereof, JP-A-53-60222, JP-A-53-66218, JP-A-53-
No. 66727, No. 55-127549, No. 56-22
No. 681, No. 57-136641, No. 58-7022
No. 1, No. 59-208540, No. 59-216136
No. 60-107641, No. 60-247237, No. 61-2148, No. 61-3137, Special Publication No. 56-18939, No. 58-1412, No. 58-1
No. 415, No. 58-6935, No. 58-108528
No. 61-3642, U.S. Patent No. 3,206,
No. 313, No. 3,317,322, No. 3,761,2
No. 66, No. 3,761.276, No. 3,850,63
No. 7, No. 3923.513, No. 4,035,185
No. 4.395,478, No. 4,504,570, European Patent No. 0.017,148, Research Disclosure Magazine No. RD16345, pages 45-46,
Same No. 18155 (issued May 1979) 265~
Core doped with metal inside as described in page 26B, same No. 23510 (issued November 1983), page 236, etc.
Examples include shell-type silver halide emulsions. In addition to silver chloride and silver bromide, typical silver halide compositions include mixed silver halides such as silver chlorobromide, silver chloroiodobromide, and silver iodobromide. The unfogged internal latent image type silver halide preferably used in the present invention does not contain silver iodide or contains less than 3% by mole of silver iodide, silver (iod)bromide, silver (iodo)chloride or silver iodide. ) is silver bromide. The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain size is taken as the grain size, and in the case of cubic grains, the grain size is taken as the ridge length, respectively, and expressed as an average based on the projected area) is 2 l or less and 0. The amount is preferably 0.1 g or more, and particularly preferably 0.151 L or more below tp. The particle size distribution may be narrow or wide, but in order to improve graininess and sharpness, the particle number or weight should be within ±40% (more preferably within ±30%, most preferably within ±30%) of the average particle size. ±2
It is preferable to use a so-called "monodisperse" silver halide emulsion in the present invention, which has a narrow grain size distribution in which 90% or more, especially 95% or more of all grains are contained in the grains (within 0%).

In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodispersed silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer having substantially the same color sensitivity. The particles can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The internal latent image type silver halide grains that are not fogged in advance used in the present invention have a cubic or octahedral shape.

regular like dodecahedron, dodecahedron
It may have a crystalline form, or it may have an irregular crystal shape such as a spherical shape, it may have a composite shape of these crystal shapes, or it may be a tabular grain. In particular, an emulsion consisting of a mixture of these various crystal forms may be used, in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more, account for 50% or more of the total projected area of the grains. There may be.

The unfogged internal latent image type silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain surface by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. can. A detailed example is 1For example, Research Disclosure Magazine No. 17
643-II (issued December 1978), page 23, etc.

The unfogged internal latent image type photographic emulsion used in the present invention contains benzene thiol for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing the photographic strip. Sulfonic acids, benzenesulfinic acids, thiocarbonyl compounds, etc. can be contained.

For further specific examples of antifoggants or stabilizers and methods of their use, see, for example, U.S. Pat.
, No. 474, No. 3,982,947, Special Publication No. 1972-2
No. 8660, RD17643 (December 1978)
VIA ~ VIM and E. J. Birr “5t
ability of Photography
ic 5ilver IlalideEmulsion
s''' (Focal Press, published in 1974).

As mentioned above, the positive-positive type silver halide color photographic light-sensitive material referred to in the present invention includes a reversal processing method, an auto-positive method, a diffusion transfer method, and the like.

Here, image formation using the autopositive method is generally achieved through the following processing steps. In other words, the photosensitive material using the auto-positive method is color development → stop → water washing → pre-bleach bath → bleach bath → water washing →
It undergoes a basic process of fixation, washing with water, stabilization, and drying. Among these, stopping, pre-bleaching bath, stabilization and subsequent water washing may be omitted, and bleaching and fixing can be performed in the 1 bath and replaced with a bleach-fix bath.

The color developing solution used here is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-methyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-
Examples include toluene sulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, and foggants such as sodium boron hydrite. agent, auxiliary developing agent such as l-phenyl-3-pyrazolidone, viscosity imparting agent, various chelating agents typified by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1
,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N
Typical examples include ``-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid), and salts thereof.

The pH of these color developing solutions is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, it is generally less than I!L per 1 m'' of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, It can be less than 300ml.When reducing the replenishment amount, it is preferable to reduce the contact area with the air in the processing tank to prevent evaporation of the solution and air oxidation, and also to prevent the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment by using means to suppress this.

The bleaching process may be carried out simultaneously with the fixing process, or the bleaching process and the fixing process may be carried out separately. Furthermore, in order to speed up the processing, it is possible to perform a bleach-fixing process after bleaching, process in two consecutive bleach-fix baths, perform a fixing process before bleach-fixing, or bleach-fix. Bleaching treatment after treatment can also be optionally carried out depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (■).
, compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds, etc. Typical bleaching agents include ferricyanide: dichromate;
organic complex salt of iron (III) or cobalt (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, l,3-diaminopropynetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. ; persulfate; bromate; permanganate; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron (m) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (10) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention, and aminopolycarboxylic acid iron (III) complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. are particularly useful in both bleach and bleach-fix solutions. PH of bleach solution or bleach-fix solution using these aminopolycarboxylic acid iron (III) complex salts
is usually 5.5 to 8, but it is also possible to process at an even lower pl (to speed up the process).

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, JP-A-53-95630, Research Disclosure No. 17129 (197
Compounds having a mercapto group or a disulfide bond as described in Jp.
Thiourea derivatives described in No. 61; JP-A-58-1623
Iodide salt described in No. 5: West German Patent No. 2,748.430
Polyoxyethylene compounds described in the No.: Special Publication No. 1973-
Polyamine compounds described in No. 8836; bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect.
In particular, U.S. Patent No. 3,893,858, West German Patent No. 1,
Preferably, the compounds described in No. 290.812 and JP-A-53-95630 are preferred;
The compounds described in No. 34 are also preferred, and these bleaching accelerators may be added to the sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the silver halide color photographic light-sensitive material of the present invention has been subjected to desilvering treatment such as fixing or bleach-fixing, it is generally subjected to a washing and/or stabilizing process. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society.
Journal of Motion Picture and Television Engineers (Journal of theSoc)
iety of Motion Picture an
d Television Engineers) No. 64
Vol. 9.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of washing water can be significantly reduced, but bacteria will grow due to the increased residence time of water in the tank.

In the processing of the color photosensitive material of the present invention, problems such as the adhesion of generated floating substances to the photosensitive material occur.As a solution to such problems, calcium and magnesium are reduced as described in Japanese Patent Application No. 61-131632. This method can be used very effectively. Also, JP-A-57-85
Isothiazolone compounds and thiabendazole compounds, chlorinated isocyanuric acid, chlorine-based disinfectants such as sodium sulfate, and other benzotriazoles described in No. 42, "Chemistry of antibacterial and antibacterial agents" by Hiroshi IJA Kuchi, Hygiene Technology Extra "Sterilization of microorganisms,
It is also possible to use the fungicides described in ``Bactericidal and Antibacterial Techniques'' and ``Encyclopedia of Antibacterial and Antibacterial Agents'' by Japan's Japan Antibacterial and Antibacterial Science.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 25 to 10 minutes.
A range of 30 seconds to 5 minutes at ~40°C is selected. Furthermore, the light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543, 58-14834,
No. 59-184343, No. 60-220345, No. 60-238832, No. 60-239784, No. 6
No. 0-239749, No. 61-4054, No. 61-1
All known methods described in No. 18749 and the like can be used. In particular, a stabilizing bath containing 1-hydroxyethylidene-1,1-disulfonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, the water washing treatment may be followed by a further stabilization treatment, such as a stabilization bath containing formalin and a surfactant used as a final bath for color photosensitive materials for photography.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Ship base type compounds described in Research Disclosure No. 14850 and Research Disclosure No. 15159, Research Disclosure No. 13
Aldol compounds described in No. 924, U.S. Patent No. 3.71
Metal salt complex described in No. 9,492, JP-A-53-1356
Examples include the urethane compounds described in No. 28.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3
- Typical compounds that may incorporate pyrazolidones are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. Also, on! of photosensitive materials! Therefore, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

The amount of replenishment in each processing step is preferably small, and the amount of replenisher is preferably O-1 to 50 times, more preferably 3 to 30 times, the amount of prebath brought in per unit area of the photosensitive material.

Further, in the present invention, the developer used when developing the black and white photosensitive material is described in Japanese Patent Application No. 1983-226292, page 66, line 7 to page 68.

Further, image formation using the reversal processing method is generally achieved by the following processing steps.

In other words, the photosensitive material using the reversal processing method is black and white development (first development) → stop → washing → reversal → washing → color development → stop → washing → adjustment bath → washing → bleaching → washing → fixing →
It undergoes a basic process of washing, stabilizing, and drying. This step may further include a prebath, a predural bath, a neutralization bath, and the like. In addition, water washing after stop, reversal 1 color development, adjustment bath, or bleaching may be omitted. The 0 reversal bath may be replaced with re-exposure, or may be omitted by adding a fogging agent to the color developing bath. can.

Zarani W! J! ! ! The bath can also be omitted.

The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-7enyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination.

The black and white developer can contain silver halide solvents such as sodium sulfite, potassium thiocyanate, and thioethers, and the preferred amount of these added is 0.1 g per 12, particularly preferably 0.5 g or more, The upper limit is the saturated dissolution amount. Moreover, it is preferable to use two or more kinds of these in combination.

In addition to the silver halide solvent, this developer contains a development inhibitor or antifoggant such as a carbon salt, a borate, a phosphate, a sulfite, a bromide, an iodide, and an organic antifoggant. be able to. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developers such as l-phenyl-3-pyrazolidone, viscosity imparting agents, polycarboxylic acid chelating agents as described in U.S. Pat. No. 4,083,723, OLS 2 ,622,
950, etc. may be included.

The steps other than black and white development in the reversal processing method are basically the same as those described above for the autopositive method.

(Effects of the Invention) According to the positive-positive type silver halide color photographic light-sensitive material of the present invention, color reproduction is improved, and the saturation and hue of the formed color positive image are more faithful to the saturation and hue of the color positive original. It has an excellent effect of reproducing the image.

In addition, this color photographic material provides more faithful color reproduction for a variety of color positive originals with different color materials, and the color positive images produced after processing will not be contaminated by residual dye. It has excellent effects.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 A color photographic material (sample 1-1) was prepared by coating a paper support laminated on both sides with polyethylene and then applying vJlZ layers starting from the first layer. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amounts in g/rn' units are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin -1,30 2nd layer (antihalation layer) Black colloidal silver -o, i.

Gelatin -0,70 3rd layer (low sensitivity red sensitive layer) Silver iodobromide spectrally sensitized with red sensitizing dyes (*l and *2) (silver iodide 5.0 mol%, average grain size 0) .4g)
-o, ts gelatin
...1.00 cyan coupler (*3) -
0.14 cyan coupler (*4) ...0.0
7 Anti-fade agent (*s, *e and *7) -0,10 Coupler solvent (*8 and *9) -0,06 4th layer (high sensitivity red sensitive layer) Red sensitizing dye (*1 and * 2) Silver iodobromide spectrally sensitized (iodide fi 6.0 mol%, average grain size 0.7).
・・0.15 Gelatin −1,00 cyan coupler (*3) ・−0,20 cyan coupler ($
4) -o,t.

Antifading agent (*5, *6 and *7) - 0,15 coupler solvent (*8 and *9) - 0,10 5th layer (intermediate layer) Magenta colloid silver - 0,02 gelatin
...1.00 color mixture prevention agent ($10
) -0,08 color mixing inhibitor solvent (*11 and $
12) -0,16 polymer latex (*13)
-0,10 6th layer (low sensitivity green sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye ($14) (silver iodide 2.5 mol%, grain size 0, 41L)
, axis 0.10 gelatin
・-0,80 magenta coupler (
*15) -0,10 anti-fading agent (*16)
+e・0.10 stain inhibitor (*17)
...0.01 stain inhibitor ($18)
・-0,001 coupler solvent (*11 and *19)-
0.15 7th layer (high sensitivity green sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye (*14) (silver iodide 3.5μ%, grain size 0.91L)
-o,t.

Gelatin -0,80 Magenta coupler (*l 5)...0.10 Antifading agent (*16) -o,l.

Stain inhibitor ($17) -0,01 Stain inhibitor (*18) -0,001 Coupler solvent (
*11 and *19)...0.15 8th layer (yellow filter layer) Yellow Coro-IM'[...0.20 gelatin
-i, o.

Mixture, color inhibitor (*10)”・0.06
Color mixing inhibitor solvent (*11 and *12) Axis-o, is polymer latex ($13) -0,10 9th layer (low sensitivity blue sensitive layer) Spectral sensitized with blue sensitizing dye ($20) Silver iodobromide (silver iodide 2.5 mol% 1 grain size 0.51L)
...0.15 gelatin
-O,SO yellow coupler ($21) ・-
0,20 Stain inhibitor (*1s) -0,0
01 coupler solvent (*9) -0,05 1st
O layer (high sensitivity blue sensitive layer) Silver iodobromide (silver iodide 2.5 mol%, grain size 1.2 μ”) spectrally sensitized with blue sensitizing dye ($20)
-0,25 gelatin
・-1,00 yellow coupler ($21)
-0,40 Stain inhibitor (*1B) -0,
002 coupler solvent (*9) -o, 1° 11th layer (ultraviolet absorbing layer) Gelatin -1,50 ultraviolet absorber (*22, *6 and *7) ...1,00 Color mixing prevention agent (* 23) -0,06 color mixing inhibitor solvent (*9), -0.15 anti-irradiation dye (*24) -0,02 anti-irradiation dye (*25) -, -0,02 12th layer (Protective layer) Fine grain silver chlorobromide (897 mol% chloride, average particle size 0
．． 2) -0,07 gelatin
...1.・50 gelatin hardener (*26
) -0,17$1 5.5'-dichloro-3,
3'-di(3-sulfobutyl)-9-ethylthiacarbocyanine Na salt *2 Triethylammonium-3-[2-(2-[3
-(3-sulfopropyl)nando(1,2-d)thiazoline-2-indenmethyl]-1-butenyl)-3-naphtho(l,z-d)thiazolino]propanesulfonate $3 2-[α-( 2,4-di-t-amylphenoxy)hexanamide]-4,6-dichloro-5-ethylphenol $4 2-[2-chlorobenzoylamide]-4-chloro-5-[α-(2-chloro -4-7-amylphenoxy)octanamide]-phenol $5 2=(2-hydroxy-3-sec-5-t-butylphenyl)benzotriazole 3 to 6 2-(2-
Human convex 5-t-butylphenyl)penzotriazole $7 2-(2-hydroxy 3,5-di-t-butylphenyl)6-chlorobenztriazole *8 Di(2-ethylhexyl) phthalate *9 Trinonyl Phosphate *102. '5-d-t-octylhydroquinone *1
1 Tricresyl phosphate *12 Dibutyl phretate *13 Polyethyl acrylate $145.5'-diphenyl-9-ethyl-3゜3'-
Disulfopropyloxacarbocyanine Na salt *157-chloro-6-methyl-2-[1-(2-octyloxy-5-(2-octyloxy-5-t-octylbenzene-sulfonamide)2-propyl] -1H
-pyrazolo[1,5-b] [1,2,4] )-riazole*16 3.3.3', 3'-tetramethyl-5゜6
．． 5',6'-tetrapropoxy-1゜1'-bisspiroindane*17 3-(2-ethylhexyloxycarbonyloxy)-1-(3-hexadecyloxyphenyl)-2
-Pyrazoline * 18 2-Methyl-5-t-octylhydroquinone * 19 Trioctyl phosphate * 20 Triethylammonium 3- [2-(3-Benzylrhodanine-5-indene)-3-benzoxazolinyl] propane sulfonate * 21 α-pivaloyl-α-[(2,4-dioxo-1-benzyl-5-ethoxyhydantoin-3-yl)-2-chloro-5-(α-2,4-di-t-amylphenoxy)butanamide] Acetanilide *225-chloro-2-(2-hydroxy-3-7-butyl-5-t-octyl)phenylbenztriazole $232.5-di-5ec-octylhydroquinone *24 *25 *261,2-bis(vinyl sulfonylacetamide)
Compounds (9) and (1) of the present invention were added to the 11th layer of ethane sample 1-1.
5), (20), (55), and (57) are added and used,
Samples 1-2 to 1-10 were prepared. Furthermore, for comparison, the compounds SO3NH4SOJNl-LI) and H2O582nm aX A-1, A-2 described in JP-A-52-2083O were added to the 11th layer, and 1-11.1-
12 were produced. In addition, Sample 1-13.1-14 was prepared by equally applying the same <A-1 and A-2 to the third and fourth layers.

Makuhe Scalar Checker with inner mold reversal film R
Photographed with DP (manufactured by Fuji Photo Film), CP-56P
The color positive film obtained by the processing was used as a color positive original, and printed on the color reversal vapors of Samples 1-1 to 1-14 by a subtractive color method. At this time, the print is made using an MMC filter to make the neutral 5 gray of the Macbeth color checker become gray with a density of 1.0 on the print.
I went there. Development processing was carried out using the process shown below. Munsell's chroma values were calculated from the measured values to examine the red, green, and blue color reproduction of the obtained images.

2. On the other hand, in order to see the degree of contamination of the image of each sample due to residual dye after processing, samples 1-1 to 1-14 were exposed through plain glass with a photosensitive needle at 500 CMS and a color temperature of 3200, and the same processed. The cyan concentration of the obtained sample was measured using a Macbeth densitometer.

The samples were processed using an automatic developing machine according to the method described below until the cumulative amount of liquid replenished was three times the tank capacity, and then measured.

Here, the first water washing and the third water washing were each performed using a countercurrent washing method. That is, the washing water is passed through the first washing (2), the overflow is led to the first washing (1), and the washing water is allowed to flow through the third washing (3), and the overflow is led to the third washing (2). The overflow of the third water wash (2) was led to the third water wash (1).

The composition of each treatment liquid was as follows.

First developer mother solution Replenisher Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid, pentasodium salt 3.0 g 3.0 g Potassium sulfite 30.0 g 30.0 g
Potassium thiocyanate 1.2g 1.2g
Potassium carbonate 35.0g 35.
0g Hydroquinone monosulfonic acid potassium 25-0g 25.0
g1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0g 2.0g
Potassium bromide 0.5g - Potassium iodide 5.0mg - Add water 1000d 1000mlpH
9,609,70 pH was adjusted with hydrochloric acid or potassium hydroxide.

Color development mother solution Replenisher benzyl alcohol 15.0d 18.
OTn[l')-t-fL"f")x-le12. Om!
14. O1'l1ii! 3.6-Sythia 1.8-octane-diol 0.20g 0.25
g Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt 0.5 g 0.5 g diethylenetriamine pentaacetic acid, pentasodium salt 2.0 g 2.0 g Sodium sulfite 2.0 g 2.5 g Hydroxylamine sulfate 3. 0g: 1.6g
N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-aminoaniline sulfate 5.0g 8.0gFluorescent brightener (diaminostilbene type) 1.0g 1.2g
Potassium bromide 0.5g - Potassium iodide 1.0mg - Add water 1000d 1000p
H10,2510,40 PH was adjusted with hydrochloric acid or potassium hydroxide.

Bleach-fix solution (mother solution and replenisher are the same) Ethylenediaminetetraacetic acid, disodium, dihydrate 5.0g Ethylenediaminetetraacetic acid, Fe(III), ammonium, lhydrate 80.0g Sodium sulfite
15.0g ammonium thiosulfate (700g/
text) 16011i2-Mercapto-1,3,4
- Triazole 0.5° Add water 10007719p H6
,50 pH was adjusted with acetic acid or aqueous ammonia.

These results are listed in Table 1 along with the layer and amount of each dye used in each sample.

According to Table 1, it can be seen that Samples 1-2 to 1-1O according to the present invention have improved color reproduction of red and green, especially green, compared to Comparative Example 1, and have extremely little staining with dye after treatment. . On the other hand, in Samples 1-11 to 1-14, although the color reproduction is relatively good, the stain due to residual dye after processing is large and the reproduction of white background is not desirable.

Example 2 Sample 1-2 of Example 1 except that the additional dye in the 11th layer and the sensitizing dye in the red-sensitive layer (3rd layer, 4th layer) were changed as shown in Table 2.
Samples 2-1 to 2-8 were prepared in exactly the same manner. In addition, Samples 2-9 to 2-11 shown in Figure 3 were prepared in the same manner.

In Samples 2-5 to 2-6, the following compound S-1 was used in place of *l as a sensitizing dye for the red-sensitive layer (third layer, fourth layer).

In Samples 2-2 to 2-8, in the same manner as in Example 1, in addition to the two dyes in the 11th layer, additional dyes related to the present invention were used to examine their effects. No additional dye was used for samples 2-1 and 2-5 and dye A- for samples 2-4 and 2-8.
3 (dye described in British Patent No. 1,521,083) was used.

It can be seen from the above results that the present invention improves color reproduction without causing a large change in sensitivity.

Example 3 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic material (Sample 3-1) was prepared in which the first to 14th layers were coated on the front side of 0IL) and the 15th to 16th layers were coated on the back side. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and the coating amount in g/rn'' units are shown below.For silver halide, the coating amount is shown in terms of silver.The emulsion used for each layer was prepared according to the manufacturing method of emulsion EMI. made.

However, as the emulsion for the 14th layer, a Lippmann emulsion without surface chemical sensitization was used.

1st layer (antihalation layer) Black colloidal silver - Axis 0. 1O Gelatin -1,30 2nd layer (medium sensitive layer) Gelatin...0.70 3rd layer (low sensitivity red sensitive layer) Spectral sensitized with red sensitizing dye (ExS-1,2,3) Silver bromide (for average particle size 0.3, size distribution (coefficient of variation) 8%, octahedral)...0.06 Spectral sensitized with red sensitizing dye (ExS-1, 2, 3) Silver chlorobromide (silver J12 5 mol%, average particle size 0.4
5g, size distribution 10%, octahedron)
...0.10 gelatin...
・1.00 cyan coupler (ExC-1) -0,1
1 cyan coupler (ExC-2) -0,10 antifade agent (Cpd-2,3,4,13 equivalents) -0,12 coupler dispersion medium (cpa-'s) -0,03 coupler solvent (Solv- 7, 2, 3 equivalents) - 0,06 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (average grain size 0. 60 le, size distribution 15%
, octahedron)・-0,14 gelatin
・-1,00 cyan coupler (ExC-1) ・-
0,15 cyan coupler (ExC-2) -0,1
5 Anti-fading agent (Cpd-2, 3, 4, 13 equivalent) -0
,15 Coupler dispersion medium (Cpd-5) ・-0,03 Coupler solvent (Solv-7, 2, 3 equivalent) -0,10 5th layer (intermediate layer) Gelatin ・-1,00 Color mixing inhibitor (Cpd -7) -0,08 color mixing inhibitor solvent (
Solv-4,5 equivalent) -0,16 Bomber Latex (Cpd-8) = -0,10 6th layer (
Silver bromide (low sensitivity green sensitive layer) spectrally sensitized with a green sensitizing dye (ExS-3)
Average particle size 0.251L, particle size distribution 8%, octahedral)...0.04 green sensitizing dye (ExS-3,4)
Silver bromide (average grain size 0.451L) spectrally sensitized with
, particle size distribution 11%, octahedral)...0.06 gelatin -0,08 magenta coupler (ExM-1,2 equivalent) antifading agent (Cpd-9)
-0,10 stain inhibitor (Cpd-10,22
Equivalent amount)...0.014 Stain inhibitor (Cpd-23) -0,001 Stain inhibitor (Cpd-12) -0,01 Force puller dispersion medium (
Cpd-5)...0.05 coupler solvent (Sol
v-4,6 equivalent)...0.15 7th layer (high sensitivity green sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3,4) (average grain size 0. 81L, particle size distribution 16%
, octahedron) -o, i.

Gelatin -0,80 Magenta coupler (ExM-1,2)...0.11 Anti-fade agent (Cpd-9) -0,10 Anti-stain agent (Cpd-xo, 22 equivalent) -0,013 Stain inhibitor (Cpd-23) - 0,001 Stain inhibitor (Cpd-12) - 0,01 Force puller dispersion medium (C
:pd-5) -0,05 coupler solvent (Solv-
4,6 equivalent) - 0,15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloidal silver - (1,20 gelatin - 1,00 color mixing inhibitor (Cp
d-7) -0,06 color mixing inhibitor solvent (Sol
v-4,5 equivalent) -0,15 Polymer latex (Cpd-8) -0,10 10th layer (intermediate layer) 11th layer (low sensitivity blue sensitive layer) same as the 5th layer Blue sensitizing dye ( Silver bromide spectrally sensitized with ExS-5,6) (average grain size 0.451L, grain size distribution 8%)
, octahedron)-0,07 blue sensitizing dye (ExS-5,6)
Silver bromide spectrally sensitized with (average grain size o, Sop,
Particle size distribution 14%, octahedral) -0,10 gelatin
-O,SO yellow coupler (E
xY-1)-0,22 stain inhibitor (Cpd-11)
-0,001 Anti-fading agent (Cpd-6) -0
,10 coupler dispersion medium (Cpd-5)...-0,0
5 coupler solvent (So 1v-2)...0.05
12th layer (high sensitivity blue sensitivity M) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 1.21L, grain size distribution 21%)
, octahedron)-0,25 gelatin
...1.00 yellow coupler (E xY -1)-
0,41 Stain inhibitor (Cpd-11) -0,002
Antifading agent (Cpd-6) -0,10 Coupler dispersion medium (Cpd-5) -0.05 Coupler solvent (Solv-2) -0,10 13th layer (ultraviolet absorbing layer) Gelatin -1, 50 Ultraviolet absorber (cpa-t, 3.13 equivalent) -1,00 Color mixing inhibitor (Cpd-6,14 equivalent) -0,06 Dispersion medium (cpct-s) -0,05 Ultraviolet absorber Agent solvent (Solv-1, 2 equivalents) -0,15 Anti-irradiation dye (Cpd-15, 16 equivalents) -0,02 Anti-irradiation dye (Cpd-17, 18 equivalents) -0,02 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.2
) - O,OS Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) - 0,02 polymethyl methacrylate particles (average particle size 2.41L), silicon oxide (average particle size 5pL) equivalent amount
-0,05 gelatin -t, S
O gelatin hardener (H-1)...0.17 15th layer (back door) Gelatin...2.50 16th layer
Layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.4
g), equivalent amount of silicon oxide (average particle size of 5 particles)
...0.05 gelatin
...2.00 gelatin hardening agent (H-1) ・
- How to make 0,11 emulsion EMI An aqueous solution of potassium bromide and silver nitrate is simultaneously added to an aqueous gelatin solution at 75°C over 15 minutes with vigorous stirring.
Octahedral silver bromide grains with an average grain size of 0.40 mm were obtained. This emulsion contains 0.3 g of 3,4-dimethyl-1 per mole of silver,
3-Thiazoline-2-thione, 6 mg of sodium thiosulfate, and 7 mg of chloroauric acid (tetrahydrate) were added sequentially to 75
Chemical sensitization treatment was performed by heating at °C for 80 minutes. The grains thus obtained were used as cores and further grown in the same precipitation environment as in the first precipitation to finally obtain an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7 pots. The coefficient of variation in particle size was approximately 10%. This emulsion, silver 1
1.5 mg sodium thiosulfate and 1.5 mg per mole
A chemical sensitization treatment was carried out by adding chloroauric acid (tetrahydrate) and heating at 60° C. for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contained 10-3% by weight of ExZK-1 as a nucleating agent based on the coating amount of silver halide, and Cp as a nucleating accelerator.
d-24 was used at 10-2% by weight. Furthermore, Alkanol XC (trade name, Dupo
nt) and sodium alkylbenzenesulfonate as coating aids, cohelic acid ester and Magef.
ac F-120 (trade name, manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-19, 20, 21) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample number A3. The compounds used in the examples are shown below.

ExS-I ExS-2 ExS-3 ExS-4 O3H pd-1 pd-2 cpcl -3 pd-4 pd-5 -(CH2-CH+-'(n-100~1000)CO
NHC4H9(tl pd-7 H pd-8 Polyethyl acrylate pd-9 pd-10 pd-11 H H C5H1l(tl Cpd-13 Cpd-14 H Cpd-15 Cpd-16 Cpd-17 Cpd-18 Cpd-19 Cpd -20 Cpd-21 H Cpd-22 XC-1 5olv-4 Tricresyl phosphate Solv-5 Dibutyl phthalate Solv-6 Trioctyl phosphate Solv-7 Di(2-ethylhexyl) sebacate 1,2-bis(vinylsulfonylacetamido)ethane xZK-1 7-[3-(5- mercaptotetrazol-1-yl)
benzamide]-10-propargyl-1,2,3,4
- Tetrahydroacridinium Velchlorate Similarly, one compound of the present invention (
19), (22), (37), and (49) were additionally applied to prepare samples 3-2 to 3-5.

Macbeth color checker on color negative film (SH)
R-100 manufactured by Fuji Photo Film) and printed on color paper (02■ manufactured by Fuji Photo Film), the same Macbeth color checker was photographed with color reversal film (RFP manufactured by Fuji Photo Film), and the original was printed in color. Two types of reflective manuscripts were prepared, one of which was disassembled using a scanner and printed. These manuscripts were exposed to light in samples 3-1 to 3-5 using ordinary reflective printing, and developed in the following processing steps to obtain color prints.

In addition, the density and color adjustment of the print was made so that the gray batch of Macbeth Ecker's Neutral 5 becomes gray with a density of 1.0 when color vapor is used as the original, and the exact same result is obtained when the original is used as printed matter. The conditions were compared.

The results obtained are shown in Table 4.

The color reproduction shown in the table has the same meaning as Example 1, and the color difference from the original is Macbeth Color Checker - 18 color glue, A, B.
Indicates the average value of color system color difference.

Processing process time Temperature Replenishment amount Color development 90 seconds 40℃ 300m1! / bleach fixing 40 seconds 38℃ 300 ml/rn'
Water washing 030 seconds 38°C Water washing ■ 30 seconds 38°C 300 d/go At this time, the replenishment ratio of the washing liquid was 8.6 times.

(Color developer) Mother solution Replenisher Ethylenediaminetetraacetic acid, disodium, dihydrate 1. Og 1.0g Sodium sulfite 2.0g 2.5g Sodium bromide 0.3g Hydroxylamine sulfate 2.6g 3. :1g Sodium chloride 3.2g 1.5g 3-methyl-4
-Amino- N-ethyl-N-hydroxyethylaniline 7.0g 9.3g Potassium carbonate 30.0g 30.0g
Fluorescent brightener (stilbene type) 1.0g 1.3
g Add pure water 1000d 100
0Tn[! pH 10,0510,90 pH was adjusted with potassium hydroxide or hydrochloric acid.

(Bleach-fix solution) (Mother solution and replenisher are the same) Ammonium thiosulfate 100g Sodium bisulfite
21.0g ethylenecyaminetetraate iron acetate m) Ammonium dihydrate 50. Add 5.0 g of Og ethylenediaminetetraate sodium acetate dihydrate to 1,000 dpi (a, s). PH was adjusted with aqueous ammonia or hydrochloric acid.

(Washing water) Pure water was used (the mother liquor and replenisher are the same). Pure water is the product in which all cations other than hydrogen ions and all anions other than hydroxide ions in tap water are reduced to ippm through ion exchange treatment. The following has been removed.

The results are shown in Table 4.

As is clear from the f54 table, according to the present invention, color reproduction is improved, and color shift (color difference) is reduced for both of the two types of color positive originals, which have large differences in color materials: color vapor and printed matter. It is clear that it is possible.

Claims (3)

[Claims] (1) It is characterized by having at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer on the support, and containing at least one dye represented by the following general formula (I). A positive-positive type silver halide color photographic light-sensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X^1 and X^2 are hydrogen atoms, cyano groups, -
OR^1, -COOR^1, -COR^1, -CONR
^1R^2, -NR^1R^2, -NR^1COR^2
, -NR^1SO_2R^2, represents an aliphatic group, aromatic group, or heterocyclic group, and Y^1 and Y^2 are each a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -NR^3R ^4, -N
Represents R^3COR^4 or -NR^3SO_2R^4, and Z^1 and Z^2 are each a hydrogen atom, a cyano group, -CO
NR^5R^6, -COOR^5, -COR^5, -N
R^5R^6, -NR^5COR^6, -NR^5SO
_2R^6-SO_2R^5, represents a sulfonic acid group, aliphatic group, aromatic group or heterocyclic group, L^1, L^2, L
^3 represents a methine group, m represents 0, 1 or 2,
M^n^■ represents an n-valent cation, where n is 1 to 3
represents an integer of R^1, R^2, R^3, R^4, R
^5 and R^6 each represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R^1 and R^2, R^3 and R^4
Alternatively, R^5 and R^6 may be connected to form a 5- or 6-membered ring. ) (2) i) The wavelength showing the maximum sensitivity of the spectral sensitization of the red-sensitive emulsion layer is on the longer wavelength side than 580 nm, and the wavelength corresponding to 30% of the maximum spectral sensitivity is on the shortest wavelength side. A wavelength is on the longer wavelength side than 560 nm, and ii) a wavelength showing the maximum spectral sensitivity of the green-sensitive emulsion layer is on the shorter wavelength side than 580 nm, and a wavelength corresponding to 30% of the maximum spectral sensitivity. 2. The positive-positive silver halide color photographic material according to claim 1, wherein the longest wavelength among the wavelengths is shorter than 590 nm. (3) i) The wavelength showing the highest spectral sensitivity of the green-sensitive emulsion layer is on the longer wavelength side than 500 nm, and the wavelength corresponding to 30% of the highest spectral sensitivity is on the shortest wavelength side. is on the longer wavelength side than 480 nm, and ii) the wavelength showing the maximum spectral sensitivity of the blue-sensitive emulsion layer is on the shorter wavelength side than 500 nm, and the wavelength corresponding to 30% of the maximum spectral sensitivity is 2. The positive-positive silver halide color photographic material according to claim 1, wherein the longest wavelength is shorter than 510 nm.